Red-violet dye and process of making same.



UNITED STATES PATENT (no ion.

ALBRECHT SCHMIDT AND ERNST BRYK. ()l llOUllST-UX-THE-BlXIX. GERMAN Y. ASSIUNORS TO FARBWERKE VORBL MEISTER LUIL'S & BRUXIXG. ()l" HotllST- X-THE-MAIN, GER- MANY. A CORPORATION OF GERMANY.

RED-VIOLET DYE AND PROCESS OF MAKING SAME.

Specification of Letters Patent.

Patented March 23, 1909.

Application filed February 20. 1907. Serial No. 358,422.

- useful Improvomcnts in liod-Yiolot llycs and wholly avoided.

Processes of Making tho Same. of which tho following is a spot-ihcat mi.

' acid dyost-utf. When purificd thoso vat dyestull's are insolublc in alkali carbonates and alkali hydrates and thus distinguish themsoircs from tho sulfonic acid dyestuffs. Whoa hoatcd with roducing agents, for instancc. with hydrosullito in alkaline solution. they dissolvo forming leuco compounds and dyo from this solution cotton and wool in \iolctrod and rod-violot tints. Those vat (l \'(Slllil may be obtainod by dissolving the arylthio- We havo fo'uud rcd-riolot dycs and a procf oss of making tho samc. said dycs boiug iulogc-n substitution products of tluoiudigo for instaucc:

(I (:0 co Cl I (:C i i It is known that phonylthioglycolic acid cannot be transformod into thioindigo by sulfuric acid. lf this acid be troatod with funung acid thou according to tho patont litorat'uro thioindigo sulfontc acid is obtained, .but no vat dyostutf. We have found that mrary to tho statomont in litoraturc rclating to phonylthioglycolic acid thoso phonyl- 2 thioglycolic acids which arc halogen substitutod in pai-a.-po;-;itimi and not substitutod in ono ortho-positiou may be transformed into \at dyostulfs if thoy aro cart-full trcutcd in tho boat with highly,conccntiatod sulfuric acid for instancc, of (36 36. or with monohydra'tc. By careful troattncut thc forum.- tion of sulfo-dyostutfs may be partly or 'lhc trcatlncut may bc charactcrizcd gouorally by boating with sulfuric acid for so long or to such tcnipcraturo, until the coloration assumed by the formed \tt'i dyostulf in sulfuric acid twcursfniostiy of a grocn tint, and not. tho coloration (mostly violet) of tho corn-s wuding sulfonic glycolic acids halogen substituted in para-- position and not substitutcd in ono orthoposltion in scVo-ral times the uautity of say conccntratrd sulfuric acid am by heating or i intensity of tho dyeing assumed by the var dyestufl' in sulfuric acid and the quantity of he alkali-insoluble n'oduct thus obtainod no longer incroaso. Tl lt" sulfuric acid, whethor of 66 Be. or monohydrato. and the temi perat-ure depend upon the nature of the substituonts; in most cast-s condcnsation is effected with monohydrato. Agents accelerating the condensation and reducing the. sulfonation may bc addcd, for instance, bisulfatc, )yrosulfatc, boric acid. phosphoric acid. chlorids, aromatic sulfuric acids and the like. A hotter yield is oftcn obtained by adding sulfur whilo condonsing. On completion of tho conth-nsation tho product of rcaction is nourod on ice: it is filtered, washed first with hot wator and thou to removeanyunattacked iarout material and small quantities of alkali-soluble bodies, with hotst-rongly dilutcsmladyc and finally washcd again with hot watt-r, until tho filtratc runs off completely colot'loss.

The paront. matorials may be obtained by known methods from the corresponding amins, for instance, by diazotizing an amin halogon-subst-ituted in para-position and not substituted in ortho- )Sitil), by combining the dinzo compount with a xanthogenatc and by treating the xanthogen est-or with chloraco t1c acid in alkaline solution, for .inr stance, 1n alcohol alkaline solution.

In this manner we have obtained a. series ol' vat tl \c tllli dyeing in the \ut. cotton and wool red of violet hue to rcd-vlolct and violet. 1- have obtained nit. dyestuffs lowing 11mins:

i tonlt. ":S a. n nm w ch t 7 v l l l \iuh-Fnwl lhu-h- -mhflu... Hrccnish Violet-It'd. Dichlonntilin Vik (3f!) Red-\iolvl K t bichlomniliutNl lgitj t. (hlur-o-toluidin (l l lzl bjij'hfcl). wbviolfl u u u fhlor-m-toluilin n'zctti 31 i tqmbwd iimm-o-tuluidin(Sik l i zjli r, t w v l -5 U u u u I-hruIn-:inilin l.\' Hi: B n A l ..V A v I n u u l (fh'mr rxylidin 'kll i'lhfl' CH3] H u u n Exam ale I. 1 mm of ar \'lthit:glycolic acid lliliflflftll-SUI)Hllilli(ti in para-position and not substituted in one ortho-positiotl. for instance, the chlot'tolylthioglycolic :tcid front chloro-o-toluitlin v .\'ll.,:(ll .,:(l-- I :2:4 is heated in the water lm-th for a short timc with 5 parts of monohydlnte n1 ('OIH'tllll'tlUti sulfuric ncitl. until the colorationand formation ot. the dycstull' no longer ithl'cnse or heated for so long or to such tcmpcruture or allowed to stand zti ordinary tctnperature that the sulfonic acid does not, assume it noticeably gray-violet coior. The product; of reaction poured into water is purified n the manner above described; on reducing in alkaline solution 1th h \'dro.-'ulfite red-violet tints are obtained on cotton and wool.

Having now described our invention, what we claim is:

I Q .The process herein dcscribed of making vat 'dyestuli's, which consists in allowing strong sulfuric .ncid to act on phcnylthioglycolie. acids halogen substituted in paraposition andnot substituted in one orthoposltion.

2, As new products. the red-violet, d yes of the general formula:

' wherein X means a halogen (Cl,Br) and R l. R the suhstitnvnts: hydrogen, halogen, methyl, being insoluble in watol', in alkalies and in dilute a ids; soluble in hot nitrohcnzomwith a vioiet-r'ed color, in (()Il(.(lll-I'tlt0(i slllitllit' acid with a greenish color, forming with an. alkaline hVtll'OSlllfitG a vat from which cotton is dyed in red-violet, and wool in clan-t-rcd shades.

1;. :1 new product, the dycstull':

lacing insultthlo in water, in :tlkalies and in dilutc acids; snltlhlc in hot nitrobenzene with Violet-red color, in concentrated sulfuric acid with grcenish color; formin with alkaline hydrosullitc a vat from'whic cotton is dyed red-violet, and wool claret-red shades.

in testimony, that we claim the foregoing as our invention, we have signed our names in presence of two subscribing witnesses.

ALBRECHT SCHMIDT. ER NS'l B R YK.

\Vitncsses: v

: JEAN GBUND, (Luu. Gnuxn. 

